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DETECTAPE - Visual Leak Detectors for Hydrogen Equipment

Presenter: Bill Hoagland – Element One John Poplawski – Midsun Specialty Products U.S. Department of Energy

DOE Host: Fuel Cell Technologies Office Will James – Safety, Codes , and Standards Program Manager th March 14 , 2016

1 | Fuel Cell Technologies Office eere.energy.gov Question and Answer

• Please type your questions into the question box

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2 | Fuel Cell Technologies Office eere.energy.gov Safety, Codes and Standards Overview Fuel Cell Technologies Office | 3

Emphasis

• R&D Activities: H2 Behavior, Risk Assessment/Mitigation, Materials Compatibility, H2 Fuel Quality, Metering, , Component Testing

• Safety Management & Resources: Hydrogen Safety Panel, Databases, and Training Props

• Outreach: Codes & Standards and Permitting, Continuous Codes and Standards Improvement, Resource Dissemination

Enable the widespread commercialization of hydrogen and fuel cell technologies through the timely development of codes and standards and dissemination of safety information NREL Testing Laboratory Fuel Cell Technologies Office | 4

• Provide independent assessment of performance • Interact with manufacturers to improve sensor performance to meet DOE 2012 targets • Support deployment with information and expertise on sensor use and performance • Test/validate new sensor R&D • Support hydrogen sensor codes and standards development (national and international) • Outreach and Education • Publications, presentations, consultations • Student Internships • Client confidentiality

The ultimate goal of the Hydrogen Sensor Testing Laboratory is to ensure that end-users get the sensing technology they need Visual Leak Detectors for Hydrogen Equipment

Presented by PRESENTERS

Bill Hoagland | Element One John Poplawski | MSP 20+ Years in Hydrogen Research 12+ Years in Silicone Manufacturing WEBINAR SUMMARY

. Company Backgrounds . Leak Detection Summary . Benefits of Low-Cost Visual Leak Detectors ™ . DetecTape H2 Technology and Performance . Applications and Markets . Availability and Upcoming Developments ELEMENT ONE BACKGROUND

. Incorporated in 2005 and began R&D of products based on core patent (U.S. Patent #6,895,805). . Key members are veterans of NREL. Collaboration with NREL 2005 - present. . Conduct thin film research in NREL’s Hydrogen Sensor Laboratory. . Funded contracts with DOE/NREL, NASA, Industry. Licensing agreements with industry. One technology license with NREL. . Four patents, three pending. . In 2015, partnered with MSP to create and market DetecTape™. www.elem1.com

DOE Recognition

March 2013 March 2012 August 2014

NREL: 2012 Industrial Growth Forum Presenting Company 2014 NREL Commercialization Assistance Program 2016 Small Business Voucher Award DETECOAT® AND DETECTAPE™

Thin films and “Smart” coatings for the detection of leaked or leaking hydrogen to achieve a new level of reliability and make possible a wide array of very low cost detection products. APPLICATIONS  Tapes and wraps

 Leak detecting pipe covers

 Safety badges and warning signs

 Leak detection coatings

 Pressure/reaction vessels and storage containers

 Sensors HYDROGEN CHARACTERISTICS

. Odorless and colorless . High propensity to leak . Low ignition energy . Invisible flame . High energy content . Lighter than air - diffuses rapidly

Difficult to Detect Leaks IMPORTANCE OF DETECTION

. Gas detection is a critical element of the safe manufacture, handling and use of many industrial . . The $700+ million gas detection market, served by more than twenty-five OEMs and hundreds of maintenance contractors, is mature and stable with a projected annual growth in the 3 to 6% range. . The global hydrogen market in 2015 was estimated at 53 million metric tons with 12% in the merchant hydrogen market with a growth rate of 5-6% per year. CURRENT LEAK DETECTION METHODS

. Bubble Testing – Simple spot . Mass Spectrometers – test method with no continuous Extremely sensitive, expensive, monitoring at low pressures. require skilled operators and . Thermal Conductivity – Works may have long response times. well in stable environments with . Gas Chromatographs – Similar minimal temperature change, to mass spectrometers and have background gas must have the same disadvantages. conductivity very different from . Ultrasonic – Technology hydrogen. improving, but cannot determine . Catalytic Combustion – exact location or whether Detects heat of combustion, combustible mixture is present. works well for low . Semi-Conducting Oxide – concentrations. Not for pure Sensor relies on surface effects hydrogen. with a minimum . Electrochemical – Sensors use concentration. Performance a liquid electrolyte, but varying degrades at lower temperatures. temperature affects gas diffusion making the sensor unreliable. THE IDEAL LEAK DETECTOR

 Very Low-cost – affordably used prolifically at potential leak sites;  Positive Indication of both the presence and the absence of hydrogen;  Simple, reliable, easily incorporated into the system, no power source;  Hydrogen specific and sensitive;  Quick response, but no false indications;  Durable, long useful life requiring little or no maintenance; and  Detectable by one or more of the human senses (sight, smell, sound). TECHNICAL APPROACHES

To meet varying requirements, Element One’s research has taken two directions: 1. Thin films that both change color and resistance for use in low cost wireless sensors; and 2. Color changing pigments for coatings for visual indication.

Vacuum deposited Synthesized multi-layer thin film nano-particles PIGMENTS VS. THIN FILMS

Pigments Thin Films Response Slower Faster Speed Manufacture Easier to produce Vacuum deposition process Detection Visual only Both visual and method resistance change Physical Incorporated into Multi-layer thin-film Structure carriers devices Material More pigment per unit Less pigment per unit required area area Durability Extremely durable, Less durable, requires resistant to selectively permeable contamination, protective coating. sunlight (UV), acids, bases, moisture. Applications Thick coatings, paints, Resistive/wireless H2 inks, wraps, molded sensors, detection of

Chemo-chromic chemical reactions: result of a partial reduction of a transition metal oxide

a partial oxidation of a catalyzed transition metal oxide pigment of < 20% effects a readily visible color change from light gray to virtually black.

CHEMO-CHROMIC RESPONSE

Transition Metal Oxide Powder (no encapsulant) RESPONSE VS. TEMPERATURE

 Responds more quickly at higher

temperatures. THRESHOLD of SENSITIVITY

 Thin film indication threshold in air is less than 400

ppm H2 RESPONSE VS. CONCENTRATION

 Speed of Response is proportional to Hydrogen

concentration. ™ DETECTAPE H2 (patent pending)

A chemo-chromic (color changing), self-fusing silicone tape designed to detect hydrogen gas (H2) leaks in storage, transmission and generation facilities. DETECTAPE™ H2 RESPONSE TEST

Gas: 5.7% H2/N2 Pigment ~ 0.004g/in2

2 Calculated H2 Req’d: ~ 0.2 ml H2 /in E1 DETECTAPE H2 TESTS . Controlled leak at ~ 0.5 ml/sec, 15 psi

150 ml 300 ml 1,800 ml

Start 5 minutes 20 minutes 60 minutes

Photo credits: Element One, Inc. So… 2 If a typical wrap of DetecTape™ H2 is 6 in ; and if it takes only .2 ml to change 1-in2….

Why does it take a leak of >300ml to completely change color? Not all leaked gas reacts with the DetecTape™ H2 pigment E1 DETECTAPE EXPOSURE TESTS (60 days and counting)

 67º C under water  south-facing outdoors (sun)  113º C in air  south-facing outdoors (shade)  126º C in air  under NaOH solution pH 10 ? 195º C in air  under HCl solution pH 2

When exposed to hydrogen, all samples except the one exposed to 195º +/-5º C turned dark within 2 minutes. A significant darkening was apparent within 1 minute. NREL TESTING OF DETECTAPE™ H2

. Test duration: 8 months (on-going)

. 55 applications of DetecTape™ H2 at NREL H2 and dispensing station . Nine clear and verified leaks were indicated . Four were “out-of-normal” requiring repair; four were “normal” (e.g., valve weep holes); one was noted for further monitoring NREL TESTING OF DETECTAPE™ H2

The deployment study was initiated with laboratory exposure testing

. Temperature cycling (-7° C to 44° C) . cycling at ambient temperature (dry to 94% rh) . Humidity cycling at elevated temperatures (56% and 75% relative humidity at 43° C) . Hydrogen exposures - after the temperature and humidity cycling,

the indicator response was verified using 5.7 vol.% H2 in N2. Result: Temperature and humidity cycling did not affect the functionality of the indicators.

NREL DEPLOYMENT STUDY NREL Deployment tests: Clear indication of a leak

Photo credits: K. Hartman/W. Buttner, NREL NREL TESTING DATA

Photo credits: K. Hartman/W. Buttner, NREL NREL TESTING DATA

. This indication was seen as the initiation of a slight darkening of the pigment. Since the color change was not as obvious as other indications, this indicator will continue to be monitored.

Photo credits: K. Hartman/W. Buttner, NREL Conclusions drawn from data by Element One

1. DetecTape™ H2 was shown to reliably identify unintended hydrogen releases from complex pneumatic systems.

2. DetecTape™ H2 was verified as a viable technology to identify small hydrogen leaks which would otherwise go undetected. The identification of such leaks facilitates implementation of appropriate corrective action before the potential occurrence of major adverse events. DETECTAPE™ H2 PRODUCTION AND MARKETING

MSP, Inc. John Poplawski Executive VP / COO MSP BACKGROUND . 1997 – Established as “Tommy Tape Manufacturing” . 2000 – Acquired by Midsun Group (est. 1992 Southington, CT), a leading provider of animal mitigation and corrosion coating products designed for electric utilities . 2006 – Renamed to Midsun Specialty Products, Inc. . 2009 – Moved operations to Berlin, CT . 40 employees . Manufacturer and distributor of self-fusing silicone tapes, corrosion protection, and specialty products worldwide

http://www.midsunsp.com CHANGES COLOR UPON DETECTION

Upon hydrogen detection, tape changes color from light grey to dark black.

. Noticeable change within 3 minutes. . Significant change within 30 minutes.

SELF-FUSING SILICONE

. Cross-linking silicone bonds to itself on contact. . Does not use adhesives, leaves no residue on substrate. . Naturally resists UV and most corrosive chemicals. . Protected by a special removable liner before installation. . Potential for vibration dampening. . Conforms smoothly when wrapped around irregular shapes.

FEATURED IN TEMPERATURE RANGE

. Extreme Temperature Range . As low as 0°F (-17°C) . As high as 350°F (176°C) . Detection reaction time may be reduced or improved depending on temperature.

** Temperature data still being collected. Subject to change **

HYDROGEN REACTION

. Silicone is a hydrogen permeable carrier for chemo-chromic pigment that changes color when exposed to hydrogen. HYDROGEN SAFETY INTEREST

. Very large quantities of hydrogen are safely used in industry today, but it’s hard to contain and difficult to detect leaks. . Hydrogen is a very large industrial commodity with a growing market. . The introduction of hydrogen as a consumer fuel has caused heightened concerns over its safety with a corresponding increased interest in hydrogen sensors. HYDROGEN REACTION

. Leak Rate and Concentration Determine Speed of Color Change. *Formula in Development* . Cumulative Effect – Slow or small leaks can lead to significant color change over a long period of time. . Reaction is permanent after hydrogen is detected, tape replacement is recommended after repair. EASY TO USE

. Can be easily installed by on-site maintenance, inspection teams or equipment operators. No certified training required. . Does not require power to operate. . Can be used in unison with existing leak detection tools including sniffers and ultrasonic detectors. INTENDED USAGE

™ DetecTape H2 can be wrapped on most objects including: . Connections, Fittings and Reducers . Swagelok and NPT . Rigid Pipeline . Flexible Tubing . Flanges . Welded Seams and Joints

INTENDED USAGE

. Initially wrap DetecTape™ H2 on all hydrogen connections that may be leak prone or susceptible to vibration damage.

. Leave DetecTape™ H2 on connections permanently or until a leak is detected and a repair needs to be made. . Can be easily removed with a blade or scissor. . Once repair is complete and connection is in working order, wrap with DetecTape™ H2 to monitor for future leaks.

USAGE LIMITATIONS

™ DetecTape H2 is not intended to:

. be used to stop nor slow down a leak. . be used to detect anything other than hydrogen gas. . prevent other gases from mixing with hydrogen. COUNTRY OF ORIGIN

™ . All components of DetecTape H2 are manufactured in the United States. . Tape core denotes Country of Origin. . Hydrogen reactive pigment synthesized in Boulder, Colorado USA. . Tape manufactured in Berlin, Connecticut USA. DOCUMENTATION

. New Product Announcement Sheet . Product Data Sheet . Safety Data Sheet . Instruction Sheet . Videos (Coming Soon) . NREL Deployment Study Coming Soon

TAPE ROLL SPEC

. Thickness – 10 mil (0.01 inch / 0.254mm) thick . Profile – Rectangular / 10 mil across . Width – 1 inch (25mm) wide . Length – 15 feet (4.57m) long . Color – No leak detected : Light grey Leak Detected : Cumulative dark black blotches . Guideline – Blue to denote Hydrogen . Current Perforation – 4 inch (10cm) strips

PERFORATION

Strips perforated to specific lengths depending on object diameter. . 1/16” – 1/8” (1mm - 4mm) diameter – 4” strip (10cm) 40-45 applications per roll NOW AVAILABLE . ¼” – ½” (6mm – 12mm) diameter – 8” strip (20cm) 25-30 applications per roll * Coming Soon * . 1” – 4” (25mm – 100mm) diameter – 12” strip (30cm) 10-12 applications * Coming Soon * . Multiple strips can be used on large diameters.

** Configurations still in trial stages. Subject to change based on user feedback ** CONTAINER

™ . DetecTape H2 15 foot rolls are shipped in a re-usable clarified polypropylene container to keep roll clean and dry while not in use. . Portable enough to fit a roll in pocket, tool belt or toolbox. USER INSTRUCTIONS

. Every roll comes with user installation and detection instructions. . More information and documentation (SDS, PDS, FAQ) is available to users on http://www.detectape.com APPLICATIONS

. Use on connections inside cabinets that are inspected on a routine schedule. . Quickly identify hydrogen leaks during inspections.

APPLICATIONS

. Use on hydrogen supply connection points in fueling stations. . Attendants and maintenance crews can react quickly with a visual alert that there is a hydrogen leak present.

APPLICATIONS

. Use on all hydrogen network connections that are within visual range of inspection routes. . Prioritize leak repair based on quantity of alerts in a zone to maximize efficiency.

APPLICATIONS

. Use on hydrogen-related research equipment to improve laboratory safety. . Once a leak is detected, equipment operator can safely shut down equipment for repair.

APPLICATIONS

. Useful in conjunction with other gas detection alarm systems. . Expedite repairs by visually identifying localized connections.

OTHER APPLICATIONS

. On-Site Hydrogen Generation . Manufacturing (, Aerospace, Etc.) . Power Plants (Using Hydrogen ) . Gas Processing and Production . Metallurgy and Welding . Portable Power Units . Pharmaceutical . And More

AVAILABILITY

. Samples available upon request through website. . Limited trial rolls available at introductory rate in exchange for user feedback and data. . Case pack – 36 rolls / case . Single rolls available with 5 roll MOQ . Available for Purchase

UPCOMING DEVELOPMENTS

. H2 Reversible Tape - Hydrogen reaction is reversible. Designed for tightly enclosed spaces where in-air hydrogen may be a concern over time.

. H2S Tape – leak detection for use as a marker for natural gas pipeline leaks. ACKNOWLEDGEMENTS

. We would like to thank the Office of Energy Efficiency and Renewable Energy’s Fuel Cell Technologies Office for their continued support. . We would like to thank Dr. William Buttner and NREL for the cooperation and assistance provided to Element One, Inc. THANK YOU FOR WATCHING Q & A SESSION

http://www.detectape.com Thank You

Presenters: •Bill Hoagland - Element One – [email protected] •John Poplawski – MSP – [email protected]

DOE Host: •Will James – Safety, Codes , and Standards Program Manager – [email protected]

Webinar Recording and Slides: (http://energy.gov/eere/fuelcells/webinars) Newsletter Signup (http://energy.gov/eere/fuelcells/subscribe-news-and-financial-opportunity- updates)

65 | Fuel Cell Technologies Office eere.energy.gov FREQUENTLY ASKED QUESTIONS

1. What range of hydrogen concentration has the tape been measured / proven with? 2. What other components have been included in the testing for Question 1? 3. What is the repeatability of the tape’s performance, i.e. does the same size leak produce color at the same rate? 4. Is there a correlation of leak amount versus color change rate? 5. What is the impact on temperature on the color change? FREQUENTLY ASKED QUESTIONS

6. What is the longest that the tape is been in use for any of the tests? 7. How can we tell if the tape is still working after it has been in service for a time? (eliminate false negatives) 8. Are there any other components that may cause false positives? 9. Are there any other components that may interfere with the hydrogen response? (eliminate false negatives) 10. Is the tape sample we received the same as will be sold for commercial use?